Process of preparing fluorodinitroethanol or fluorodinitromethane from fluorotrinitromethane



United States Patent "ice 3'446857 Patented May 27, 1969 formaldehyde will yield FDNOL via an unstable FDM 3,446,857 intermediate phase. By excluding aldehydes from the PROCESS OF PREPARING FLUOR reaction, however, FDM may be obtained. In the re- ETHANOL 0R FLUORODINITROMETHANE m-ainder of this specification, FTM, FDM and FDNOL FROM FLUOROTRINITROMETHANE Horst G Adolph Silver spring M d assignor to the 5 will be used to designate fluorotrinitromethane, fluorodinitromethane and fluorodinitroethanol, respectively. 33%? g s; Amenca as represented by the secre The reduction procedure of FTM is specific, that is, N Drawing Filed Jul 31 19 4 s 7 55 the redudtion of other halotrinitromethanes, such as Int. Cl. (107d 31/34, 33/ chlorotrinitromethane and bromotrinitrornethane in the US. Cl. 260-633 8 Claims 10 presence of base, does not produce the corresponding 0 dinitro compound. Instead, it has been found that such The 1nvent1on described herem may be manufactured reduction procedure, except in the case of FTM, merely and used by or for the Government of the United States results in the loss of halogen.

of America for governmental purposes without the pay- The invention will be more fully understood by referment ofany royalties thereon or therefor. 5 ence to the following examples which are intended only ThlS 1nvent1on relates to novel methods for the preparato more fully illustrate the invention and are not to be tion of fluorine-containing an nitro-containing aliphatic construed as limitations thereon. compounds. Specifically, the invention is directed to novel methods for the preparation of fluorodinitrometh- Examp 16 I ane, and fluorodinitroethanol. 20 This example illustrates the preparation of FDM from In the past, fiuorodinitroethanol has been prepared by FTM.

the aqueous fluorination of sodium or potassium dinitro- To a solution of 5 g. of FTM in 10 ml. of methanol ethanol, which was in turn obtained from nitromethane there was added, dropwise at -10 C., a mixture of 6.7

via mononitropropanediol and dinitropropanediol. This g. of 30% hydrogen peroxide and a solution of 3.3 g. of

procedure was, however, rather tedious and, moreover, KOH in 15 ml. of methanol. A precipitate formed and,

dinitropropanediol is not readily obtained. after completion of the addition, the mixture was poured It has now been unexpectedly found that fluorodinitrointo ice-cold dilute sulfuric acid and the resulting soluethanol may be prepared in high yield by the reduction tion extracted with methylene chloride. The extracts were of fluorotrinitromethane with hydrogen-peroxide in the dried over magnesium sulfate and the solvent was dispresence of a base and formaldehyde. It has further been tilled off. The residue, distilled in vacuo, gave 1.5 g. (41% found that, in the absence of aldehyde, the reduction of of theoretical) of FDM, the purity by gas chromatofluorotrinitrornethane will yield fluorodinitromethane. graphic analysis being approximately 85% Accordingly, the objects of this invention are:

(1) The preparation of fluorodinitroethanol from Examples H N fiuorotrinitromethane and Examples II through IV, presented in tabular form in (2) The preparation of fiuorodinitromethane from Table I, below, illustrate the preparation of FDM from fluorotrinitromethane. FTM under varying reaction conditions.

TABLE I.PREPARATION OF FDM FROM FTM Materials Conditions Products Example:

2 5 g. FTM in 10 m1. OHaOH, 6.7 g. ca. 30% H202 and base mixed and added to FTM 1.5 g. (41%) of ca. 85% pure FDM.

H202, 3.3 g. KOH in 15 ml. CHsOH. at 10 C. in 15 min. then poured into ice/dil. sulfuric acid. 3 5 g. FTM in 15 m1. CHzClg, 3.3 g. KOH in First base, then H202 added to CHzCla 2.7 g. of a mixture, containing 31% FDM.

15 ml. CH OH, 4 g. 30% H202. soln. at 10 C. in 15 min. then poured into ice/dil. sulfuric acid. 4 5.4 g. FTM in 15 ml. aqueous CHQOH H 0; added at 20 C. in 15 min. to mix- 1.4 g. (35%) FDM;pnr1ty ca. 85%.

3.7 g. KOH in 15 ml. same solvent, 4.4 g. ture of FTM and base. Drowned immw 30% H202. diately, without allowing mixture to warm up.

The ob ects of the mventron are accomplished v1a gen- Example V eral reaction scheme of the invention which may be illustrated as follows: This example illustrates the preparation of FDNOL from FTM. FTM An amount of 175 ml. of 30% aqueous hydro-gen per- %;,g \Egg; formaldehyde oxide (1.5 mole and 140 ml. of 37% aqueous formaldehyde solution (1.7 mole) were placed in a two-liter flask FDM FDM (Intennediate) and cooled in an ice bath to 5 C. About 1 ml. of a solution of 29 g. sodium hydroxide (0.72 mole) in 1 ml. water i was added to the mixture with stirring, causing the tem- FDNOL perature to rise to about 15 C. With continued cooling, 280 ml. methanol were added and the temperature was wherem: 65 brought to 5 C. An amount of g. FTM was then FTM is fluorotrinitromethane, placed in the flask, an ice-salt bath being used to effect FDM is fluorodinitrom th cooling. The remaining 179 ml. sodium hydroxide were FDNOL is fluorodinitroethanol, then added over a period of 20-25 minutes and dilute GENERAL PROCEDURE sulphuric acid was added after completion of the addition 7 of the base. Upon addition of the acid, the temperature As may be seen from the reaction scheme illustrated rose to about 20 C. The solution was then saturated with above, the alkaline reduction of FTM in the presence of sodium chloride and extracted with methylene chloride.

3 The extract was dried and distilled to obtain 69 g. (75% theoretical) of FDNOL; B.P. 53-56" C. Purity, by gas chromatography, was 88%.

Examples VI-XI Examples VI through XI, set forth in tabular form in Table II, below, further illustrate the preparation of FDNOL from FTM under varying reaction parameters and reactant concentrations.

TABLE IL-PREPARATION OF FDNOL FROM F'IM Materials per g. FTM

H202 (EH MeOH NaOH (ml.) (ml.) (ml.) (g. 1111111. 1120) 20 7 20 6. 6 KOH, 4O 30 50 4. 7, 30 30 30 4. 7, 30 20 20 40 3. 3, 20 20 20 40 3. 2, 20 18 18 32 3.1 18.5

Conditions Yield of FDNOL, percent Base added below 10 to mixture of others... Ca. 40. Base added at 5-10" in 40 min Ca. 65. Base added below 0 in 30 min purity 81 mole percent. Base added at ca.-0 in 30 min. 81; purity 82 mole percent. Base added at 05 in 30 min 80; purity 85 mole percent.

Base added at ca. 5 in 20-25 min 81.5; purity 85 mole percent.

As stated previously, the alkaline reduction of the fluorotrinitromethyl group to the fluorodinitromethyl group was unexpectedly found to be specific to the compounds instantly illustrated (i.e. FIM and EDM) and, for best results, the solution should be at about pH 8 and at a temperature of from 0-5 C. Broadly, the temperature may range from as low as 20 C. to about 15 C.

Although water may be used as the reaction diluent, satisfactory results may be obtained by using Water miscible diluents such as acetone and alcohol.

The reducing agent which is used in combination with alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, is hydrogen peroxide although other reducing agents such as potassium iodide and sodium arsenite may also be used in the practice of the invention.

Aldehydes which may be used in the instant invention are any of the commonly known aliphatic aldehydes and dialdehydes such as formaldehyde, acetaldehyde, etc.

Obviously, many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that, Within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Having thus described the invention, what is claimed and desired to be secured by Letters Patent of the United States is:

1. The method of preparing fluorodinitromethane which comprises reacting fluorotrinitromethane with a reducing comprises, reacting a solution of fiuorotrinitromethane in methanol with a reducing agent selected from the group consisting of hydrogen peroxide, potassium iodide and sodium arsenite in the presence of an alkaline medium.

4. The process of claim 3 wherein said alkaline medium is selected from the group consisting of sodium hydroxide and potassium hydroxide.

5. The process of claim 4 wherein the temperature during said reaction is maintained between about 20 C. and 15 C.

6. The process of preparing fiuorodinitroethanol which comprises reacting fiuorotrinitrornethane with a reducing agent selected from the group consisting of hydrogen peroxide, potassium iodide and sodium arsenite in the presence of a base, formaldehyde and methanol.

7. The process of claim 6 wherein said base is selected from the group consisting of sodium hydroxide and potassium hydroxide.

8. The process of claim 7 wherein the temperature during said reaction is maintained between about 20 C. and 15 C.

References Cited UNITED STATES PATENTS 3,127,736 4/1964 Bost et al 35.4

LELAND A. SEBASTIAN, Primary Examiner.

US. Cl. X.R. 

1. THE METHOD OF PREPARING FLUORODINITRAMETHANE WHICH COMPRISES REACTING FLUOROTRINITROMETHANE WITH A REDUCING AGENT SELECTED FROM THE GROUP CONSISTING OF HYDROGEN PEROXIDE, POTASSIUM IODINE, AND SODIUM ARSENITE IN A AN ALKALINE MEDIUM.
 2. THE METHOD FOR PREPARING FLUORODINITROETHANOL WHICH COMPRISES REACTING FLUOROTRINITROMETHANE WITH A REDUCING AGENT SELECTED FROM THE GROUP CONSISTING OF HYDROGEN PEROXIDE, POTASSIUM IODIDE, AND SODIUM ARSENITE IN THE PRESENCE OF A BASE AND FORMALDEHYDE. 